JP2002294213A - Surface modifier - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface modifier which can allow the surface of a film- forming material, such as ink and coating material, and a molding material to exhibit excellent lubricity, scratch resistance, water repellency and chemical resistance, the modifier adhering firmly to the surface so as not to readily lose surface-modifying effects, while exhibiting surface-modifying effects equivalent to those of the conventional ones, particularly the modifier being not washed away by a hot-water treatment and the like. SOLUTION: The surface modifier comprises a polyester composite resin (A) formed by reacting a monool (a) containing a 25-200C hydrocarbon, a polybasic acid (b) and a polyhydric alcohol (c).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a surface modifier comprising a composite resin obtained by chemically bonding a monool containing a hydrocarbon having 25 to 200 carbon atoms to a polyester or polyurethane. More specifically, the present invention relates to a surface modifier capable of exhibiting excellent lubricity, scratch resistance, water repellency, and chemical resistance on the surface of a film-forming material such as ink or paint or a molding material.

[0002]

2. Description of the Related Art Conventionally, many methods are known as methods for modifying the surface of inks and paints, for example. For example,
There is a method of improving the properties of the surface by covering the surface of the coating film by lifting (bleeding) the modifier from the coating material onto the coating film surface. This method is used in a wide variety of applications in a general manner. As a modifier used for this,
Examples include natural oils and fats such as carnauba wax and palm oil, fatty acids such as stearic acid, silicone oil, polyethylene, polypropylene, and Teflon-based synthetic waxes.

[0003] However, in the case of the surface modified by this method, the effect is not maintained for a long time or the effect is obtained under severe conditions because the modifier is merely raised on the surface. There was a problem of being lost. Specifically, the modifier may be washed away by hot water treatment such as retort treatment, or the modifier may be peeled off by severe friction.

[0004] In particular, in recent years, environmental problems in factories and attempts at zero emission have become active. Correspondingly, when the material subjected to the surface modification by the conventional method is subjected to the hot water treatment, contamination of the treated hot water due to the loss of the modifying agent has been regarded as a problem.

[0005]

Therefore, while exhibiting the same surface modification effect as the conventional product, it adheres firmly to the surface and does not easily lose the modification effect. There is a need for a surface modifier that does not.

[0006]

Means for Solving the Problems The present inventors have solved the above-mentioned problems by using a composite resin obtained by chemically bonding a polyolefin and a polyester or a polyurethane as a surface modifier. The inventors have found the present invention. This is the excellent lubricity of the polyolefin part,
Properties mainly related to surface modification such as scratch resistance, water repellency, and chemical resistance, and ink / polyester / polyurethane parts
The characteristic of the modified material is that it has the property of firmly adhering to a substrate such as a paint.

Specifically, a polyester / polyurethane material to be a polyester / polyurethane portion is chemically bonded starting from a hydroxyl group of a monol (a) containing a hydrocarbon having 25 to 200 carbon atoms to be a polyolefin portion. A surface modifier composed of a polyester / polyurethane composite resin.

That is, the present invention relates to a polyester composite resin (A) obtained by reacting a monool (a) containing a hydrocarbon having 25 to 200 carbon atoms, a polybasic acid (b), and a polyhydric alcohol (c). A surface modifier.

Further, the present invention provides a polyester composite resin (B) obtained by reacting a monol (a) containing a hydrocarbon having 25 to 200 carbon atoms, a carboxylic anhydride (d), and an epoxy group-containing compound (e). )).

The present invention further relates to a monool (a) containing a hydrocarbon having 25 to 200 carbon atoms and a polyfunctional isocyanate compound.
The present invention relates to a surface modifier comprising a polyurethane composite resin (C) obtained by reacting (f) and an alcohol (g) other than (a).

Further, the present invention relates to a film-forming material comprising a main agent and the surface modifier according to any one of claims 1 to 3.

Further, the present invention relates to a molding material comprising a main agent and the surface modifier according to any one of claims 1 to 3.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The monool (a) containing a hydrocarbon having 25 to 200 carbon atoms in the present invention has one hydroxyl group in one molecule.
And polyolefin such as polyethylene and polypropylene, or carbon number such as polybutadiene
It has up to 25 to 200 linear or branched, saturated or unsaturated hydrocarbon groups.

Specifically, there are polyethylene monool, polypropylene monool, polybutadiene monool and the like, and these are not particularly limited even if they are primary, secondary and tertiary alcohols. However, primary alcohols are most preferable in consideration of the reaction efficiency when converting into polyester or polyurethane and the surface modification effect.

The carbon number of the hydrocarbon group contained in the monol (a) is preferably from 25 to 200, more preferably from 35 to 150. When the number of carbon atoms is less than 25, properties as a polyolefin are not exhibited. On the other hand, if the number of carbon atoms exceeds 200, the properties of the polyolefin become too strong, and it is difficult to obtain the effect as a composite material.

The polybasic acid (b) in the present invention is a substance which forms a polyester with the hydroxyl group of the monol (a). If these are listed, for example, saturated and unsaturated dicarboxylic acids such as phthalic acid, methylphthalic acid, succinic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, methylcyclohexanedicarboxylic acid and the like; Examples include acid anhydride, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, citric acid, polycarboxylic acids such as ethylene glycol bistrimellitate and glycerol tristrimellitate, and acid anhydrides thereof. Furthermore, cyclopentadiene-
Also included are polybasic acids obtained by Diels-Alder reaction of unsaturated compounds having a conjugated double bond with unsaturated dicarboxylic acids, such as maleic acid adducts, terpene-maleic acid adducts, and rosin maleic acid adducts. .

Of these, the use of dicarboxylic acids and their anhydrides more preferably improves the properties of the resulting composite resin.

The polyhydric alcohol (c) in the present invention includes diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol and butylene glycol;
Examples include triols such as glycerin and trimethylolpropane, and polyhydric alcohols such as diglycerin, triglycerin, pentaerythritol, dipentaerythritol, mannitol, and sorbite.

In the synthesis of the polyester composite resin (A), the mixing ratio of the polybasic acid (b), the polyhydric alcohol (c) and the monool (a) is such that 1 mol of the polybasic acid (b) is mixed with 1 mol of the polyhydric alcohol.
(c) is about 1 mol, preferably 0.8 to 1.2 mol, and monool (a) is 0.01 to 2 mol. When the blending ratio of the monool (a) is more than 2 moles per 1 mole of the polybasic acid (b), the molecular weight of the ester portion of the obtained polyester composite resin (A) becomes smaller, and conversely, less than 0.01 mole. If so, the average molecular weight of the ester portion of the obtained polyester composite resin (A) becomes too large, and in any case, the characteristics as the composite resin cannot be obtained.

The carboxylic acid anhydride (d) in the present invention has one or more carboxylic acid anhydride groups in one molecule. For example, phthalic anhydride, 2-methylphthalic anhydride, 3-methylphthalic anhydride, trimellitic anhydride, cyclohexanedicarboxylic anhydride, methylcyclohexanedicarboxylic anhydride, methylhymic anhydride, methylcyclohexene Dicarboxylic anhydride, pyromellitic anhydride, ethylene glycol bis trimellitate, glycerol tristrimellitate,
Succinic anhydride, maleic anhydride, glutaric anhydride, butylsuccinic anhydride, hexylsuccinic anhydride, octylsuccinic anhydride, dodecylsuccinic anhydride, butylmaleic anhydride, pentylmaleic anhydride, hexylmaleic acid Anhydride, octylmaleic anhydride, decylmaleic anhydride, dodecylmaleic anhydride, butylglutamic anhydride, hexylglutamic anhydride, heptylglutamic anhydride, octylglutamic anhydride, decylglutamic anhydride, dodecylglutamic anhydride And the like.

The carboxylic anhydride (d) is preferably a compound having one carboxylic anhydride group in one molecule,
It is preferable in terms of the properties of the obtained polyester composite resin (B).

The epoxy group-containing compound (e) in the present invention
Are those having one or more epoxy groups in one molecule. For example, as a compound having one epoxy group in one molecule, an aromatic ring such as glycidyl (meth) acrylate, vinyl glycidyl ether, styrene oxide, phenyl glycidyl ether, sec-butylphenyl glycidyl ether, cresyl glycidyl ether, etc. Or an alicyclic-containing epoxy group-containing compound, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether,
Examples include pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, dodecyl glycidyl ether, and the like.

Compounds having a plurality of epoxy groups include bisphenol A diglycidyl ether, 3,4-
Epoxycyclohexylmethyl-3,4, -epoxycyclohexanecarboxylate (Union Carbide Co., Ltd.``Siracure UVR-6110 '' etc.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide ( Union·
Carbide `` ELR-4206 '' etc.), limonene dioxide
(Daicel Chemical Industries, Ltd., `` Celoxide 3000 '' etc.), allylcyclohexene dioxide, 3,4, -epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxycyclohexyl-5,5-spiro -3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate (such as Union Carbide's `` Siracure UVR-6128 ''), bis (3,4-epoxycyclohexylmethyl) adipate, Bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane and the like can be mentioned.

As the epoxy group-containing compound (e), a compound having one epoxy group in one molecule is preferable in view of the properties of the obtained polyester composite resin (B).

In the synthesis of the polyester composite resin (B), the compounding ratio of the acid anhydride (d), the epoxy group-containing compound (e) and the polyolefin monol (a) is such that the epoxy compound is mixed with 1 mol of the acid anhydride (d). The group-containing compound (e) is almost 1 mol, preferably 0.8 to 1.2 mol, and the polyolefin monol (a) is 0.1 mol.
01 to 2 moles. When the blending ratio of the polyolefin monol (a) is more than 2 moles per 1 mole of the acid anhydride (d), the resulting polyolefin / polyester composite resin
Polyester composite resin (B) obtained when the molecular weight of the ester portion of (B) becomes smaller, and conversely, becomes less than 0.01 mol
The average molecular weight of the ester portion becomes too large, and in any case, the characteristics as a composite resin cannot be obtained.

The polyfunctional isocyanate compound (f) in the present invention is a compound having two or more isocyanate groups in one molecule. The isocyanate compound (f) is a substance that reacts with the hydroxyl group of the monol (a) and the alcohol (g) to form a urethane bond. To list these,
For example, toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, diphenyl ether diisocyanate, xylene diisocyanate, tolidine diisocyanate, dianisidine diisocyanate, isopropylidene bis (phenylisocyanate ) And other linear diisocyanates, such as tetramethylene diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate, isophorone diisocyanate, norbornene diisocyanate, and dicyclohexylmethanediamine. Cyclic aliphatic diisocyanates such as isocyanate, dicyclohexyl ether diisocyanate, and isopropylidene bis (cyclohexyl isocyanate); and triphenyl Methane triisocyanate, bis
(Diisocyanatotolyl) trifunctional or higher functional isocyanate compounds such as phenylmethane, and polymers of the above isocyanates such as polyphenylmethane isocyanate.

Of these, the use of a diisocyanate compound is preferred because the molecular weight of the polyurethane portion can be easily controlled.

Alcohol (g) other than (a) in the present invention
Is a compound containing one or more hydroxyl groups in one molecule.
The alcohol (g) is a substance constituting the polyurethane portion together with the isocyanate compound (f). Alcohol (g) is a different element from monol (a).

That is, while the monool (a) is a portion constituting the polyolefin portion of the polyurethane composite resin, the alcohol (g) is used for constituting the polyurethane portion together with the isocyanate compound (f). . Therefore, the molecular weight and urethane bond density of the polyurethane part can be adjusted by using the polyfunctional alcohol (g-1), and the isocyanate terminal can be blocked or modified by the monofunctional alcohol (g-2).

The polyfunctional alcohol (g-1) which can be used as the alcohol (g) includes diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, butylene glycol, glycerin, and trimethylolpropane. Triols, such as diglycerin, triglycerin, pentaerythritol, dipentaerythritol,
Polyhydric alcohols such as mannitol and sorbite, and polymerized polyols such as polycaprolactone, polyethylene glycol, polypropylene glycol, and polyester polyols are also included. Among these, diols are particularly preferable because the molecular weight of the polyurethane portion can be easily controlled.

The monofunctional alcohol (g-2) that can be used as the alcohol (g) is not particularly limited as long as it contains one hydroxyl group in one molecule. Examples thereof include aliphatic monools such as methanol, ethanol, propanol, butanol, lauryl alcohol, and stearyl alcohol; aromatic monools such as phenol, naphthol and benzyl alcohol; and alkylene glycol ether monols such as propylene glycol monomethyl ether. .

In addition, it is possible to modify the polyurethane part by using a compound having another functional group other than a hydroxyl group in the alcohol (g). For example, for the purpose of introducing a double bond, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerin mono (meth) acrylate, glycerin di (meth) acrylate, glycerin divinyl ether, pentaerythritol tri (meta ) Acrylate, pentaerythritol trivinyl ether, trimethylolpropanedi
Unsaturated alcohols such as (meth) acrylate, trimethylolpropane divinyl ether, and divinylphenol can also be used.

Monool during synthesis of polyurethane composite resin
The composition ratio of (a), the polyfunctional isocyanate compound (f), and the alcohol (g) other than (a) is important for controlling the ratio of the polyolefin portion to the polyurethane portion of the polyurethane composite resin. In addition, the ratio of the polyfunctional alcohol (g-1) to the monofunctional alcohol (g-2) of the other alcohol (g) is also important for controlling the molecular weight of the polyurethane part, and depends on the molecular weight of the target polyurethane part. Should be adjusted accordingly. However, in consideration of the stability over time of the polyurethane composite resin after the completion of the reaction, it is preferable that the remaining isocyanate groups are eliminated. For this reason,
With respect to the total amount of hydroxyl groups contained in the monol (a) and the alcohol (g), it is preferable to add at least an equivalent or more to the isocyanate of the isocyanate compound (f).

Further, the polyester composite resins (A) and (B)
Both the polyolefin portion and the ratio of the polyester portion, when the carbon number of the polyester portion is 0.1 to 10 times the carbon number of the polyolefin portion, especially when it is 0.2 to 5 times, the polyolefin-polyester composite resin The characteristics appear prominently.

The preferred ratio of the polyolefin part to the polyurethane part of the polyurethane composite resin (C) is, when the average carbon number of the polyurethane part is 0.1 to 10 times the carbon number of the polyolefin part, particularly 0.2 to 5 times. When the ratio is twice, the characteristics of the polyurethane composite resin appear remarkably.

The synthesis of the polyester composite resin (A) is performed by a known general ester synthesis method, and is not particularly limited. When the reaction involves a dehydration reaction, for example, if water is removed with an azeotropic solvent, the reaction proceeds efficiently.

The reaction temperature is preferably such that the polyolefin monol (a) is melted or dissolved in a solvent, since the molecular weight of the polyester portion can be easily controlled.

The synthesis of the polyester composite resin (B) is carried out, for example, by the method described in JP-A-61-126128. That is, acid anhydride (a), epoxy group-containing compound
A predetermined amount of (b) and the hydroxyl group-containing compound (c) are placed in a reaction vessel, and the synthesis is carried out using a heater that can be controlled with a uniform temperature distribution. It is preferable to carry out the reaction in a molten state when synthesizing without a solvent, and in a dissolved state when containing a solvent, since the molecular weight of the polyester portion can be easily controlled.

The reaction temperature of the polyester composite resins (A) and (B) is 80 to 200 ° C., preferably 90 to 160 ° C.

In synthesizing the polyester composite resins (A) and (B), conventionally known catalysts used for general esterification, for example, sodium hydroxide, potassium hydroxide,
Requires basic catalysts such as salts such as lithium chloride, diethyl zinc, tetra (n-butoxy) titanium, amines such as triethylamine, N, N-dimethylbenzylamine and triphenylamine, or acid catalysts such as paratoluenesulfonic acid Can be used according to

When synthesizing the polyester composite resins (A) and (B), a general radical inhibitor such as hydroquinone or triethylamine may be used for the purpose of protecting against inadvertent gelation during the reaction. it can.

The synthesis of the polyurethane composite resin (C) is performed by a known general polyurethane synthesis method, and is not particularly limited. In particular, it is preferable to carry out the reaction at a reaction temperature in which the monool (a) is melted or dissolved in a solvent because the molecular weight of the polyurethane portion can be easily controlled.

The reaction temperature during the synthesis of the polyurethane composite resin (C) is 60 to 200 ° C., preferably 80 to 160 ° C.

When synthesizing the polyurethane composite resin (C), a conventionally known catalyst used for general urethanization, for example, a metal compound such as dibutyltin laurate, tin dioctylate or lead dioctylate, triethylamine , N, N-dimethylbenzylamine, triphenylamine, and other amines can be used as needed.

In synthesizing the polyurethane composite resin (C), a general radical inhibitor such as hydroquinone and triethylamine can be used for the purpose of protecting the gel from inadvertent gelation during the reaction.

Further, it reduces residual isocyanate,
Alternatively, in order to control the molecular weight of the polyurethane portion, known amines and carboxylic acids can be added as needed.

The amines may be any of primary, secondary and tertiary amines, and are not particularly limited to monoamines, diamines, triamines and polyamines containing more amino groups.

As the carboxylic acids, monocarboxylic acids,
There is no particular limitation on dicarboxylic acids, tricarboxylic acids, or polycarboxylic acids containing more carboxyl groups.

The surface modifier in the present invention includes ink,
A material that improves the performance of its surface to a property different from that of the main agent by adding the modifier to the main agent such as a coating material or a molded product such as a paint and exposing the modifier to the surface. . For example, excellent lubricity, scratch resistance, water repellency,
It is intended to improve water resistance and chemical resistance.

The polyester composite resin of the present invention
(A), (B) and polyurethane composite resin (C) are obtained as a solid or a viscous body at room temperature. When these are to be blended as a surface modifier, they may be used by dissolving them in the main agent, or when they cannot be dissolved, they may be added in the form of fine particles.

The addition amount is 0.1 to 30% by weight, preferably 0.5 to 15% by weight in the medium to be added. When the addition amount is small, the surface modification effect becomes thin, and when the addition amount is large, the base material becomes brittle.

In particular, when the fine particles are added to the film-forming material, a higher effect can be obtained by increasing the average particle diameter of the film-forming material to be larger than the dry film thickness.

The film-forming material in the present invention refers to a material for forming a film by printing or coating a substrate. For example, ink, paint, and the like correspond to this.

The use of the film forming material in the present invention is not particularly limited, and can be used for all uses. For example, gravure ink, flexographic ink, silk screen ink, offset ink, overprinting varnish, paint, primer, anchor coat, filling varnish, finishing varnish, and the like can be given. Among them,
When used for a coating material constituting the outermost surface of the coating film layer, that is, for a surface printing ink, an overprinting varnish, a finishing varnish, etc., the effect of the surface modifier is remarkable because it is preferable.

Further, as a material requiring friction resistance after coating and curing, for example, a paint for a food container such as a beverage can, a food can, a beverage / food paper pack, a paint for a precoated steel sheet, and a paint for a processed paper. It is preferably used. Among them, paints for cans such as beverage cans, food cans, and cosmetic cans that require high friction resistance,
Particularly, it is suitably used as a paint for beverage cans. When used as a paint for cans, it is subjected to hot water treatment such as retort treatment and past treatment for sterilization and can washing after filling the contents, so that the effect of the modifier of the present invention can be maximized. .

There is no particular limitation on the method of forming a film using these film forming materials. For example, a printing machine such as an offset printing machine, a gravure printing machine, a screen printing machine, and a flexographic printing machine; a coating machine such as a roll coater, a curtain coater, a dip coater, and a knife coater; or a spray coating or a brush coating.

At the time of film formation of these film-forming materials, heat drying or after-baking can be performed. The heating temperature greatly varies depending on the type and purpose of the film forming material, the type of the base material, and the method of forming the film. These heating is preferably 50-300 ° C, more preferably 100 ° C
When carried out at ~ 250 ° C, the effects of the present invention are maximized. It is considered that this is because melting of the composite materials (A) to (C) occurs, and further, the affinity between the ester and urethane portions and the main agent of the film forming material is improved.

The base material of these film forming materials can be used without any particular limitation. These categories vary widely. As the main resin component of the film forming material main agent,
Polyester resin, polyurethane resin, epoxy resin,
Acrylic resin, phenol resin, cellulose resin such as nitrocellulose, ketone resin, polyamide resin, amino resin, vinyl chloride resin, vinyl acetate resin, polyvinyl alcohol resin, polystyrene resin, polyvinyl ether resin, polyvinyl butyral resin, polyether resin, Examples include alkyd resin, polybutadiene resin, xylene resin, guanamine resin, diallyl phthalate resin, furan resin, polyimide resin, maleic acid resin, melamine resin, urea resin and the like. These are roughly classified into a thermoplastic resin and a thermosetting resin depending on the configuration, and any of them can be used.

Many of the film forming material base agents are diluted with a solvent in consideration of film formation. As the solvent contained in the film forming material base material, for example, hexane,
Hydrocarbon solvents such as cyclohexane, octane, toluene, xylene and methylcyclohexane; ester solvents such as ethyl acetate, propyl acetate, butyl acetate and methyl propylene glycol monoacetate; acetone, methyl ethyl ketone, methyl butyl ketone, cyclohexanone, methyl cyclohexanone Ketone solvents, diethyl ether, methyl butyl ether, methyl propylene glycol, propyl glycol monoether, diethylene glycol monobutyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, tetrahydrofuran, dioxane and other ether solvents, methanol, ethanol, propanol, butanol, cyclo Aliphatic alcohol solvents such as hexanol, phenol,
Aromatic alcohol solvents such as cresol, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, dichloroethylene, trichloroethylene, tetrachloroethylene, chlorobenzene, dichlorobenzene and other halogen solvents, industrial gasoline, solvent naphtha, petroleum ether, petroleum naphtha, petroleum benzine And petroleum solvents such as mineral spirits, vegetable solvents such as turpentine oil, and water.

Further, it can also be used for radiation curing type reactive solvent dilution type such as ultraviolet ray and electron beam curing type. In this case, a reactive solvent mainly using acrylates, epoxy monomers, or the like is used for dilution.

The molding material in the present invention refers to a material used as a material for molding by the following processing method. For example, compression / transfer molding, hand lay-up molding, spray-up molding, vacuum / pressure bag molding, autoclave molding,
Cold press molding, injection molding, extrusion molding,
Examples include a hollow molding method, a calendar molding method, a foam molding method, a solid molding method, and a powder molding method.

The main material of the molding material can be used without any particular limitation. These categories vary widely. The main resin components of the molding material base are polyester resin,
Cellulose resins such as polyurethane resin, epoxy resin, acrylic resin, phenol resin, cellulose acetate, nitrocellulose, ketone resin, polyamide resin, vinyl chloride resin, vinyl acetate resin, polyvinyl alcohol resin, polystyrene resin, polyvinyl ether resin, polyvinyl butyral Resin, polyether resin, alkyd resin, polybutadiene resin, amino resin, xylene resin, guanamine resin, diallyl phthalate resin, furan resin, polyimide resin, maleic acid resin, melamine resin, urea resin, and the like. These are roughly classified into a thermoplastic resin and a thermosetting resin depending on the configuration, and any of them can be used. In particular, in the case of a molded product made of a thermoplastic resin, an excellent effect appears.

[0063]

The present invention will be specifically described below.

Example 1 Synthesis of Polyester Composite Resin (A) Monool (a), polybasic acid (b), and polyhydric alcohol (c) were weighed in a 1-liter three-necked flask equipped with an azeotropic tube as shown in the following table. And then add 100 ml of toluene and 1 hydroquinone
g was added and heated to 155 ° C. in an oil bath. Cool after 6 hours,
The solvent was removed under reduced pressure to obtain a polyester composite resin (A).

The obtained composite resin was added to 2-propanol to adjust the solid content to 25% by weight, and the mixture was dispersed or dissolved by a high-speed mixer.

In the table, the notation of alcohol (a) indicates that C25 is polyethylene monol having an average carbon number of 25. Also. The number in the parentheses after the weight indicates the number of moles of each material added. The carbon number ratio is (1
The value of carbon number of ester part in molecule / (carbon number of alkyl part) was shown. Table 1----------------------No. Alcohol (a) Polybasic acid (b) Alcohol ( c) Carbon number ratio------------------------------------Example 1.1 C25 184 g (0.5) PAH 222 g (1.5) EG 96g (1.5) 1.2 Example 1.2 C25 92g (0.25) PAH 370g (2.5) EG 160g (2.5) 4.0 Example 1.3 C25 46g (0.13) PAH 370g (2.5) EG 160g (2.5) 8.0 Example 1.4 C25 31g (0.08) PAH 370g (2.5) EG 160g (2.5) 12.0 Example 1.5 C50 359g (0.5) PAH 148g (1.0) EG 64g (1.0) 0.4 Example 1.6 C50 359g (0.5) PAH 222g (1.5) EG 96g (1.5) 0.6 Example 1.7 C50 180g (0.25) PAH 370g (2.5) EG 160g (2.5) 2.0 Example 1.8 C50 184g (0.5) MAH 147g (1.5) EG 96g (1.5) 1.2 Example 1.9 C50 184g (0.5) ADA 219g (1.5) EG 96g (1.5) 1.0 Example 1.10 C50 184g (0.5) PAH 222g (1.5) PG 117g (1.5) 0.7 Example 1.11 C50 184g (0.5) PAH 222g (1.5) DEG 159g (1.5) 1.4 Comparison Example 1.1 C12 93 g (0.5) PAH 222 g (1.5) EG 96 g (1.5) 2.5 −−−−− ------------------------------------------------------------------------------------------- PAH: phthalic anhydride, MAH: maleic anhydride, ADA: adipic acid, EG: ethylene glycol Recall, PG: propylene glycol, DEG: diethylene glycol Example 2 Synthesis of polyester composite resin (B) Monool (a), carboxylic anhydride (d), and epoxy group-containing compound (e) were placed in a 1-liter three-necked flask. Charge with the weights in the table below, and add 200 ml of toluene and 1 hydroquinone.
g, 0.5 g of N, N-dimethylbenzylamine, and 1
Heated to 20 ° C. After cooling for 6 hours, the solvent was removed under reduced pressure to obtain a polyester composite resin (B).

The obtained composite resin was added to 2-propanol to adjust the solid content to 25% by weight, and the mixture was dispersed or dissolved by a high-speed mixer.

In the table, the notation of alcohol (a) indicates that C25 is a polyethylene monol having an average carbon number of 25. Also. The number in the parentheses after the weight indicates the number of moles of each material added. Also. The number in the parentheses after the weight indicates the number of moles of each material added. Further, the carbon number ratio is (the number of carbon atoms in the ester portion in one molecule of the composite resin) /
(The number of carbon atoms in the alkyl moiety in one molecule of the composite resin). Table 2----------------------No. Alcohol (a) Acid anhydride (d) Epoxy ( e) Carbon number ratio--------------------------------Example 2.1 C25 184 g (0.5) PAH 222 g (1.5) GMA 213g (1.5) 1.8 Example 2.2 C25 92g (0.25) PAH 185g (1.25) GMA 178g (1.25) 3.0 Example 2.3 C25 46g (0.13) PAH 185g (1.25) GMA 178g (1.25) 6.0 Example 2.4 C25 23g (0.06) PAH 185g (1.25) GMA 178g (1.25) 12.0 Example 2.5 C50 359g (0.5) PAH 222g (1.5) GMA 213g (1.5) 0.9 Example 2.6 C50 179g (0.25) PAH 185g (1.25) GMA 178g (1.25) 1.5 Example 2.7 C50 90g (0.13) PAH 185g (1.25) GMA 178g (1.25) 3.0 Example 2.8 C75 153g (0.33) PAH 148g (1.0) GMA 142g (1.0) 0.6 Example 2.9 C75 214g (0.20) PAH 148g (1.0) GMA 142g (1.0) 1.0 Example 2.10 C120 340g (0.20) PAH 89g (0.6) GMA 85g (0.6) 0.38 Example 2.11 C120 104g (0.12) PAH 178g (1.2) GMA 170g (1.2) 1.31 Implementation Example 2.12 C50 359 g (0.5) MAH 147 g (1. 5) GMA 213g (1.5) 0.9 Example 2.13 C50 359g (0.5) HPAH 231g (1.5) GMA 213g (1.5) 1.8 Example 2.14 C50 359g (0.5) PAH 222g (1.5) PGE 213g (1.5) 0.9 Example 2.15 C50 359 g (0.5) PAH 222 g (1.5) DGE 324 g (1.5) 2.5 Comparative Example 2.1 C12 93 g (0.5) PAH 222 g (1.5) GMA 213 g (1.5) 3.8 −−−−−−−−−−−−−−−−− -------------------------------------------------------------------------------------------------------------------- DGE: decyl glycidyl ether Example 3 Synthesis of Polyurethane Composite Resin Monool (a) and isocyanate compound (f) shown in Table 1 were charged into a 1-liter three-necked flask equipped with a cooling tube at a weight shown in the following table. Further, 200 ml of toluene, 1 g of hydroquinone and 0.5 g of tin dioctylate as a reaction catalyst were added, and the mixture was heated to 120 ° C. in an oil bath. After the reaction, it was confirmed that the residual isocyanate value obtained by calculation from the respective composition ratios was reached, and the polyfunctional alcohol (g-1) shown in Table 1 was further confirmed.
Was added. Further, after confirming that the isocyanate value was obtained by calculation from the respective composition ratios, an excess amount (10 equivalents or more) of 2-propanol was further added as a monofunctional alcohol (g-2). After confirming that there was no residual isocyanate by an infrared absorption spectrum, the solvent was removed under reduced pressure to obtain a polyurethane composite resin.

The obtained composite resin was added to 2-propanol to adjust the solid content to 25% by weight, and the mixture was dispersed or dissolved by a high-speed mixer.

In the table, the notation of alcohol (a) is, for example, C25
Represents that it is a polyethylene monol having an average carbon number of 25. Also. In parentheses after the weight is stated,
The number of moles of each material is shown. Further, the carbon number ratio is represented by a value of (average carbon number of urethane portion in one molecule) / (average carbon number of alkyl portion). Table 3 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− No.Alcohol (a) Isocyanate (f) Alcohol (g -1) Carbon number ratio-------------------------------------Example 3.1 C25 184 g (0.5) HMDI 168 g (1.0) EG 31 g (0.5) 0.8 Example 3.2 C25 184 g (0.5) HMDI 252 g (1.5) EG 62 g (1.0) 1.2 Example 3.3 C25 92 g (0.25) HMDI 210 g (1.25) EG 62 g (1.0) 2.0 Example 3.4 C25 46g (0.13) HMDI 210g (1.25) EG 70g (1.13) 4.0 Example 3.5 C25 23g (0.06) HMDI 210g (1.25) EG 70g (1.19) 8.0 Example 3.6 C25 12g (0.03) HMDI 210g (1.25) EG 76g (1.22) 16.0 Example 3.7 C50 359g (0.5) HMDI 252g (1.5) EG 62g (1.0) 0.6 Example 3.8 C50 90g (0.13) HMDI 210g (1.25) EG 70g (1.13) 2.0 Example 3.9 C50 44g (0.06 ) HMDI 210g (1.25) EG 74g (1.19) 4.0 Example 3.10 C75 67g (0.06) HMDI 210g (1.25) EG 74g (1.19) 2.7 Example 3.11 C120 104g (0.06) HMDI 210g (1.25) EG 74g (1.19) 1.7 Example 3.12 C50 359 g (0.5) IPDI 333 g (1 .5) EG 62g (1.0) 1.7 Example 3.13 C50 180g (0.25) IPDI 278g (1.25) EG 62g (1.0) 2.8 Example 3.14 C50 90g (0.13) IPDI 278g (1.25) EG 70g (1.13) 5.6 Example 3.15 C50 90g (0.25) HMDI 210g (1.25) HDO 118g (1.0) 2.7 Example 3.16 C50 90g (0.25) HMDI 210g (1.25) DEG 106g (1.0) 2.4 Example 3.17 C50 90g (0.25) HMDI 210g (1.25) TEG 245g (1.0) 2.7 Example 3.18 C50 90g (0.25) HMDI 210g (1.25) PEG 620g (1.0) 4.9 Example 3.19 C50 90g (0.25) HMDI 210g (1.25) DCP 228g (1.0) 4.0 Example 3.20 C50 90g (0.25) HMDI 210g (1.25) TCP 228g (1.0) 5.1 Comparative Example 3.1 C12 47g (0.25) HMDI 210g (1.25) EG 62g (1.0) 4.1 −−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−− HMDI: hexamethylene diisocyanate, IPDI: isophorone diisocyanate, EG: ethylene glycol, HDO: hexanediol, DEG: diethylene glycol, TEG: triethylene glycol, PEG: polyethylene glycol (n = 10), DCP: dicap Lactone, TCP: tricaprolactone Example 4 Evaluation of Polyester Composite Resin (A) as Lubricant The composite resin synthesized in Example 1 and dispersed in 2-propanol (solid content 25% by weight) was prepared using ACRYLOID AT -400
(Acrylic resin manufactured by ROHM & HAAS) 20% by weight, CARGILL 5770
20% by weight (polyester resin manufactured by CARGILL), 20% by weight of Mycoat 106 (amino resin manufactured by Mitsui Cytec), 20% by weight of butyl cellosolve, 15% by weight of Solvesso 100 (petroleum solvent manufactured by Exxon Chemical), 2-propanol 5 Amount described in metal coating composed of% by weight (solid content of composite resin)
The mixture was mixed and sufficiently stirred with a mixer. After completion of the stirring, a chromate-treated aluminum metal plate was coated using a bar coater # 8, dried and baked in a gas oven at 200 ° C. for 4 minutes, and then subjected to a hot water paste treatment at 80 ° C. for 30 minutes. Further, the dynamic friction coefficient of the obtained coating film in a three-point support method with a load of 1 kg was measured.

The polyethylene wax used in Comparative Example 4.3 was obtained by subjecting polywax 725 (polyethylene manufactured by Baker Petrolite) to a dispersion treatment in the same manner as in Example 1. Table 4 −−−−−−−−−−−−−−−−−−−−−−−−− No.Composite resin (A) Amount added (% by weight) Friction coefficient −−−−−−−−− −−−−−−−−−−−−−−−−−−− Example 4.1 Example 1.1 2 0.045 Example 4.2 Example 1.2 2 0.062 Example 4.3 Example 1.3 2 0.083 Example 4.4 Example 1.4 2 0.087 Example 4.5 Example 1.5 2 0.042 Example 4.6 Example 1.6 2 0.035 Example 4.7 Example 1.7 2 0.049 Example 4.8 Example 1.8 2 0.042 Example 4.9 Example 1.9 2 0.048 Example 4.10 Example 1.10 2 0.051 Example 4.11 Example 1.11 2 0.039 Example 4.12 Example 1.6 0.3 0.052 Example 4.13 Example 1.6 1 0.046 Example 4.14 Example 1.6 20 0.072 Example 4.15 Example 1.6 35 0.082 Comparative Example 4.1 None 0 0.185 Comparative Example 4.2 Comparative Example 1.1 2 0.138 Comparative Example 4.3 PE Wax 2 0.099 Comparative Example 4.4 Palm Oil 2 0.152 −−−−−−−−−−−−−−−−−−−−−−−− Example 5 Polyester Composite Resin (B )of Evaluation synthesized in Example 1 as agent, a composite resin prepared by dispersing in 2-propanol (solid content 25 wt%), ACRYLOID AT-400
(Acrylic resin manufactured by ROHM & HAAS) 20% by weight, as CARGILL
5770 (polyester resin manufactured by CARGILL) 20% by weight, Mycoat 106 (amino resin manufactured by Mitsui Cytec) 20% by weight
Butyl cellosolve 20% by weight, Solvesso 100 (Exxon Chemical's petroleum-based solvent) 15% by weight, 2-propanol 5% by weight
Was mixed with the paint for metal composed of the above (in terms of the solid content of the composite resin) and sufficiently stirred with a mixer. After the completion of the stirring, a chromate-treated aluminum metal plate was coated using a bar coater # 8, dried and baked in a gas oven at 200 ° C. for 4 minutes, and then subjected to a hot water paste treatment at 80 ° C. for 30 minutes. Further, the dynamic friction coefficient of the obtained coating film at a load of 1 kg was measured.

The polyethylene wax used in Comparative Example 5.3 was obtained by subjecting a polywax 725 (a polyethylene manufactured by Baker Petrolite) to a dispersion treatment in the same manner as in Example 1. Table 5 −−−−−−−−−−−−−−−−−−−−−−−−−− No.Composite resin (B) Addition amount (% by weight) Friction coefficient −−−−−−−−− −−−−−−−−−−−−−−−−−−− Example 5.1 Example 2.1 2 0.039 Example 5.2 Example 2.2 2 0.044 Example 5.3 Example 2.3 2 0.065 Example 5.4 Example 2.4 2 0.084 Example 5.5 Example 2.5 2 0.021 Example 5.6 Example 2.6 2 0.028 Example 5.7 Example 2.7 2 0.033 Example 5.8 Example 2.8 2 0.022 Example 5.9 Example 2.9 2 0.026 Example 5.10 Example 2.10 2 0.038 Example 5.11 Example 2.11 2 0.029 Example 5.12 Example 2.12 2 0.028 Example 5.13 Example 2.13 2 0.026 Example 5.14 Example 2.14 2 0.024 Example 5.15 Example 2.15 2 0.032 Example 5.16 Example 2.5 0.3 0.042 Example 5.17 Example Example 2.5 1 0.034 Example 5.18 Example 2.5 20 0.063 Example 5.19 Example 2.5 35 0.066 Comparative Example 5.1 None 0 0.185 Comparative Example 5.2 Comparative Example 2.1 2 0.118 Comparative Example 5.3 PE Wax 2 0.099 Comparative Example 5.4 Oil 2 0.152 Example 6 Evaluation of polyurethane composite resin (C) as a lubricant Synthesized in Example 3 Then, the composite resin prepared by dispersing in 2-propanol (solid content: 25% by weight) was mixed with ACRYLOID AT-400.
(Acrylic resin manufactured by ROHM & HAAS) 20% by weight, as CARGILL
5770 (polyester resin manufactured by CARGILL) 20% by weight, Mycoat 106 (amino resin manufactured by Mitsui Cytec) 20% by weight
Butyl cellosolve 20% by weight, Solvesso 100 (Exxon Chemical's petroleum-based solvent) 15% by weight, 2-propanol 5% by weight
Was mixed with the paint for metal composed of the above (in terms of the solid content of the composite resin) and sufficiently stirred with a mixer. After the completion of the stirring, a chromate-treated aluminum metal plate was coated using a bar coater # 8, dried and baked in a gas oven at 200 ° C. for 4 minutes, and then subjected to a hot water paste treatment at 80 ° C. for 30 minutes. Further, the dynamic friction coefficient of the obtained coating film at a load of 1 kg was measured. Table 6 −−−−−−−−−−−−−−−−−−−−−−−−−− No.Composite resin (A) Amount added (% by weight) Friction coefficient −−−−−−−−− −−−−−−−−−−−−−−−−−−− Example 6.1 Example 3.1 2 0.052 Example 6.2 Example 3.2 2 0.046 Example 6.3 Example 3.3 2 0.055 Example 6.4 Example 3.4 2 0.058 Example 6.5 Example 3.5 2 0.067 Example 6.6 Example 3.6 2 0.074 Example 6.7 Example 3.7 2 0.048 Example 6.8 Example 3.8 2 0.045 Example 6.9 Example 3.9 2 0.053 Example 6.10 Example 3.10 2 0.039 Example 6.11 Example 3.11 2 0.044 Example 6.12 Example 3.12 2 0.051 Example 6.13 Example 3.13 2 0.054 Example 6.14 Example 3.14 2 0.066 Example 6.15 Example 3.15 2 0.048 Example 6.16 Example 3.16 2 0.046 Example 6.17 Example Example 3.17 2 0.049 Example 6.18 Example 3.18 2 0.058 Example 6.19 Example 3.19 2 0.049 Example 6.20 Example 3.20 2 0.056 Example 6.21 Example 3.7 0.3 0.080 Example 6.22 Example 3.7 1 0.056 Example 6.23 Example 3.7 20 0.063 Example 6.24 Example 3.7 35 0.082 Comparative Example 5.1 None 0 0.185 Comparative Example 5.2 Comparative Example 3.1 2 0.123 Comparative Example 5.3 PE Wax 2 0.099 Comparative Example 5.4 Palm Oil 2 0.152 −−−−−−−−−− Example 7 Evaluation of Composite Resin (A to B) as a Lubricant and Drying Temperature Synthesized in Examples 1 and 2, and in 2-propanol (Solid content 25% by weight), and the composite resin prepared was dispersed in ACRYLOID AT-40.
0 (Acrylic resin manufactured by ROHM & HAAS) 20% by weight, CARGI
20% by weight of LL 5770 (polyester resin manufactured by CARGILL), 20% by weight of Mycoat 106 (amino resin manufactured by Mitsui Cytec)
Butyl cellosolve 20% by weight, Solvesso 100 (Exxon Chemical's petroleum-based solvent) 15% by weight, 2-propanol 5% by weight
Was mixed with 2% by weight (in terms of the solid content of the composite resin) of the metal coating composed of, and sufficiently stirred with a mixer. After the completion of stirring, a chromate-treated aluminum metal plate is coated using a bar coater # 8, and dried and baked in a gas oven at the temperature (unit: ° C) and time (unit: minute) shown in Table 7 A hot water paste treatment was performed at 80 ° C. for 30 minutes. Further, the dynamic friction coefficient of the obtained coating film at a load of 1 kg was measured. Table 7 −−−−−−−−−−−−−−−−−−−−−−−−−− No.Composite resin Temperature (° C) Time (min) Friction coefficient −−−−−−−−−− ------------------------------------------------------------------ 200 4 0.035 Example 7.5 Example 1.6 270 2 0.039 Example 7.6 Example 2.5 40 120 0.126 Example 7.7 Example 2.5 80 90 0.087 Example 7.8 Example 2.5 150 15 0.033 Example 7.9 Example 2.5 200 4 0.021 Example 7.10 Example 2.5 270 2 0.038 Comparative Example 7.1 Palm Oil 40 120 0.233 Comparative Example 7.2 Palm Oil 80 90 0.196 Comparative Example 7.3 Palm Oil 150 15 0.149 Comparative Example 7.4 Palm Oil 200 4 0.152 Comparative Example 7.5 Palm Oil 270 2 0.160 ---- Example 8 Evaluation of Polyester Composite Resin (A) as Friction Resistance Improver Synthesized in Example 1 and 2 -Professional The composite resin prepared by dispersing in Nord (solid content 25 wt%), manufactured by Arakawa Chemical KL424
(Solvent-type polyurethane), and the mixture was mixed in the amount described (in terms of solid content of the composite resin) and sufficiently stirred with a mixer. After the completion of the stirring, the film was applied to a biaxially stretched PET film (corona treatment) using a bar coater # 5 and dried with a dryer.

A vibration-resistant friction tester (load: 500 g, 100
(Reciprocating, high quality paper) was evaluated for friction resistance. The abrasion resistance was evaluated on a five-point scale, 5: no change, 4: partially scratched, 3: entirely scratched, 2: partially peeled coating film. ,
1: Almost all of the coating film was peeled. Table 8 −−−−−−−−−−−−−−−−−−−−−−−−−− No.Composite resin (A) Addition amount (wt%) Evaluation −−−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−.− (−) Example 8.1 Example 1.5 2 4 Example 8.2 Comparative Example 3.1 2 1 Comparative Example 8.3 PE Wax 22-3 Comparative Example 8.4 Palm Oil 2 2--------------------------Example 9 Evaluation as an acid resistance improver in a molding material The composite resin prepared by dispersing in 2-propanol (solid content 25% by weight) synthesized in Example 1 was subjected to 2-
The propanol was removed, dried and powdered. The obtained composite resin powder was kneaded with Acrypet V (acrylic resin for molding manufactured by Mitsubishi Rayon Co., Ltd.) using a twin-screw extruder at a stated amount of 230 ° C., and a 5 mm-thick sheet was further extruded with a 230 ° C. extruder. Prepared.

The obtained sheet was cut into a width of 8 cm and a height of 20 cm to obtain a sample piece. This sample piece was subjected to an exposure test for 240 hours (water injection time: 12 minutes per hour) using a carbon arc sunshine weather meter equipped with a water spray.

The exposed test piece was immersed in a 5N aqueous sulfuric acid solution and allowed to stand at room temperature for 24 hours, and then the sample piece was taken out and washed with water.

The degree of damage caused by acid on the surface was visually evaluated on a five-point scale. 5: No change, 4: Light cloudiness is observed, 3:
White turbidity is observed. 2: Strong white turbidity is observed.

The polyethylene wax used in Comparative Example 9.3 was obtained by subjecting polywax 725 (polyethylene manufactured by Baker Petrolite) to dispersion treatment in the same manner as in Example 1, and further dispersing the powder in the same manner as in Example 9. Table 9 −−−−−−−−−−−−−−−−−−−−−−−−− No.Composite resin (A) Addition amount (% by weight) Evaluation −−− Example 9.1 Example 1.5 5 4 Example 9.2 Example 1.6 5 4 Example 9.3 Example 1.7 5 4 Comparative Example 9.1 None 0 1 Comparative Example 9.2 Comparative Example 3.1 5 1 Comparative Example 9.3 PE Wax 5 2-------------------------------

[0078]

The polyester obtained by chemically bonding a polyolefin and a polyester or a polyurethane.
By using a polyurethane composite resin as a surface modifier for blending with a film-forming material such as ink or paint or a molding material, the surface modifier was not easily lost from its surface. That is, by using the surface modifier of the present invention, the surface modification effect can be maintained even under severe conditions such as the conventional hot water treatment and strong friction.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C10M 107/32 C10M 107/32 107/44 107/44 C10N 50:02 C10N 50:02 50:08 50:08 F term (reference) 4H104 CB13A CE13A QA08 QA12 RA01 4J029 AA03 AB07 AC03 AE11 BA03 BA04 BA05 BA08 BF09 BF18 CA02 CA04 CA06 CB04A CB04B CD04 FA02 FC03 FC05 FC08 FC29 FC35 FC36 GA13 GA14 GA17 HA04E02 J03 H03J02 H03E CA02 CA03 CA04 CA05 CB01 CB03 CB04 CB05 CB07 CC03 CC07 CC12 CC13 CC61 CC62 DA01 DB01 DB03 DB04 DF01 DF12 DG03 DG04 DP12 DP19 FA02 FC01 FC03 HA01 HA07 HA13 HC03 HC12 HC13 HC22 HC46 HC52 HC53 HC64 HC67 HC70 HC71 HC73 BA1 4 CF031 DA061 DB001 DD001 DD042 DF001 DG001 DG042 DG052 DG262 DH001 DJ011 NA04 NA07 NA11 PC02 PC10

Claims (5)

[Claims] 1. Monool containing a hydrocarbon having 25 to 200 carbon atoms.
A surface modifier comprising a polyester composite resin (A) obtained by reacting (a), a polybasic acid (b), and a polyhydric alcohol (c). 2. Monool containing a hydrocarbon having 25 to 200 carbon atoms.
(a), carboxylic anhydride (d), and epoxy group-containing compound
A surface modifier comprising the polyester composite resin (B) reacted from (e). 3. Monool containing a hydrocarbon having 25 to 200 carbon atoms.
(a), a polyfunctional isocyanate compound (f), and a polyurethane composite resin obtained by reacting an alcohol (g) other than (a)
A surface modifier comprising (C). 4. A film-forming material comprising a main agent and the surface modifier according to any one of claims 1 to 3. A molding material comprising a main agent and the surface modifier according to any one of claims 1 to 3.